Production of ethylene hydrocarbons



Patented Aug. 9, 1932 a marine Tr s Tau ALEXANDER 1r. mn'xrmonn ion VERoELLIfITA'IJY, iAssrGN'o'a fro EEHEFNAUGKIUEK CHEMICAL COMPANY, or NAUGATUCK, comacrrcne, A om oimmzon or coitmurmur rnonuorroiv or ETHYLENEIEYDRGCARBOWS This case is a division of my -applicaition "Serial No. 109,961, filed May 18, 1926; now Patent No; 1,752,016yiss-uedMarch*25,'1930.

'tivity. lArccording to-the present invention the introduction of a third metal into the amalgam greatly increases the acti-vity thereof andat the s-am'e time permits carrying out reactions which are impossible with-alumialum activated by the usual methods. The metal introduced into the ordinary iilumlnum-mercury amalgam is preferably-Zinc. Other metals, such as cadmium mayalso be employed. WVhile the invention isnot limited to any particular method of torming 't-he reagent, the 7 following may serve as illustrations The amalgam may :be conducted by the use of soluble sa'lts o'f mercury 1 and of the third metal, these salts being precipitated -upon lalum-mum :which is immersed or sus pendedin the-solutionof these salts. An-

- othermethod of forming-the ainalgam of 'this inventionis to melt the aluminum and third metal -together=thus forming an alloy which may *then be ground to any desired "degree and subsequently amalgamated I on its the p'lycolate thus obtained bemtreated with water, a; glycol and aluminum hydroxide are obtained;

*Whe'n aceton'e is'treated' with the improved reagent the end product will be te'tramet h yl ethylene glycol or pinacol.

It th'e amount of third:metal be increased to'from 'l to SOZZJJoy weight ofthe aluminum, o

ethylene hydrocarbons are produced -=when *ketones' are treated. For= example acetone will yield propylene: 3on "oo 0H +2AL1= p The above equations "describe fre aeti'o'ns which take place in 1a non-aqueous medium. If :wateribeintroduced into the reacting mixture, nascent hyd'ro'g en is' 'evolved." This nascent hydrogen 'Will lead tO the formation of a series or" reduction 'produ'cts. "Under-such conditions keton'es will i produce second ar-y c CH CHTO'H''CH ilhe' improved aeti vated a luniinuln reagent --may'be prepared by*amalgamating an alloy "of aluminum "and a'nothe'r *metaL'mr'eiEeraM-y zin'c. In thisinstance --the' amalgamis preparedaccording to the-standard practiceof forming' m'erc'ury' anml-gams'tf+maa1s.' Amalgams 'made-iwith mercury and pure aluminum {are subject to the"-'-disadvant-ag'"e that the layer of al'gam is rather "easily detached "during the reaction and frequently the reaction stops as the result of this: With zinc present in the amalgam layer a viscous tacky material is formed in which, the zinc may act as a. cementing substance to keep the aluminum and mercury together. By increasing the percentageof zinc, say up to in the aluminum zinc alloy, alarge percentage of propylene will appear in the reaction when acetone is used as the startin material. When an alloy contains 7% o zinc, propylene continues to appear in large quantities in this reaction. When the amount of zinc is reduced to'2% or less, very little propylene will appear, and pinacone is ob- .rough shavings. 7 experience of orgamc chemlsts that not all above-mentioned foreign product.

employed, and the aluminum may be used in the form of filings or even in the form of Moreover it has been the makes of pure aluminum may be employed in carrying out these catalytic reactions. In-

deed it is the general experience that there is but one kind of aluminum a product made in Germany which will yield pinaconeas the product of the reduction of acetone. By practicing the present invention, however, any :kind of aluminum may be employed and even better results obtained than with the The percentage of zinc present in the alloy may be to been possible.

varied within wide limits, depending upon the product desired. For the production of pinacone approximately 3% or less of zinc .willgive excellent results'. If propylene or other ethylene hydrocarbons are desired, a higher amount of zinc, even up to 30%, may be used to advantage, although quantities of the unsaturated hydrocarbon will be obtained with 7% of zinc. It is understood, of course, that the percentage of zinc is figured to metallic zinc. If a zinc compound is employed, calculations are made accordingly. For example zinc chloride will analyze a little less I than of Zinc as metal. It will'thus be seen that the reduction of organic oxygencontaining substances particularly the ketones and other compounds which are ordinarily reduced by nascent hydrogen formed by amalgamated aluminum in the presence of water, can be carried out much more economically and with better results than has hither- Furthermore the invention acting material.

the amalgam.

essential to have the aluminum in a very finely divided state. Instead of zinc, cadmium may be employed in the same manner.

The production of ethylene glycols and ethylene hydrocarbons, and the reduction-or conversion of ketones and their derivatives serve as illustrations of some of the uses to which the improved aluminum amalgam may be put. It will be understood,'however, that the reagent may bevariously employed in reduction reactions in the presence of water, as well as in reactions Where the aluminum forms a compound with all or part of the re- The'claims are therefore to be interpreted broadly. The expressions metallic element, metal and zinc? as used in the claims, are descriptive of these materials as, single elements, or where theyare available assuch for the purposes of the invention, and the percentages given in the claims refer to percentages of the metal, not

of its salt. It is to be understood therefore that salts of zinc and the other metals which may be employed are comprehended by the claims. I

Having thus described my invention, what I claim and desire to protect by Letters Pattent is: 1. In the production of ethylene hydrocarbons from ketones, the stop of subjecting said ketones to the action of aluminum amalgam containing another metallic element selected from the group consisting of zinc and cadmium said metallie'element being present in the amalgam in excess of 3% and not greater than 30% by weight of the aluminum in 2. In the production of ethylene hydrocarbons'from ketones, the step of subjecting said ketones to the action ofaluminum amalgam containing another metallic element in excess of 3% selected from the group consist ing of zincand cadimum.

3. In the production of ethylene hydrocarbons from ketones, the step of subjecting said ketones to the action'of aluminum amalgam containing zinc in excess of 3%.

4:. A method for the production of propyl- 'ene from acetone, which comprises treating acetone with an aluminum amalgam containing more than approximately 3% of zinc.

iSigned at Turin, Italy, this 25th day of September, 1929. 1

"ALEXANDER T. MAXIMOFF.

possesses the advantage that any type of aluminum can be employed and that it is not 

